Fibre-reactive dyes, their preparation and their use

ABSTRACT

Reactive dyes of formula (1) wherein Q 1  and Q 2  are each independently of the other hydrogen or unsubstituted or substituted C 1 -C 4 alkyl, A is the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore, X is halogen, 3- or 4-carboxypyridin-1-yl, or 3- or 4-carbamoylpyridin-1-yl, Y is vinyl or a radical —CH 2 —CH 2 —U and U is a group removable under alkaline conditions, and q is the number 1 or 2, are suitable for dyeing and printing cellulosic or amide-group-containing fiber materials.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the National Phase of International ApplicationPCT/EP2013/060759 filed May 24, 2013 which designated the U.S. and whichclaims priority to European Pat. App. No. 12172247.4 filed Jun. 15,2012. The noted applications are incorporated herein by reference.

The present invention relates to fibre-reactive dyes, to processes forthe preparation thereof and to the use thereof in dyeing or printingtextile fibre materials.

The practice of dyeing and printing using reactive dyes has recently ledto higher demands being made of the quality of the prints and theprofitability of the dyeing and printing process. As a result, there isstill a need for novel reactive dyes having improved properties,especially in respect of their application.

Nowadays reactive dyes are required that have sufficient substantivityand at the same time have good ease of washing off of unfixed dye. Theyshould also have a good tinctorial yield and high reactivity, theobjective being to provide especially dyeings and prints having highdegrees of fixing. The known dyes do not satisfy these requirements inall properties.

The problem underlying the present invention is accordingly to find, forthe dyeing or printing of fibre materials, novel improved reactive dyeshaving the qualities characterised above to a high degree. The noveldyes should especially be distinguished by good build-up behaviour, highfixing yields and high fibre-dye binding stability; it should also bepossible for dye that is not fixed to the fibre to be washed off easily.The dyes should also yield dyeings and prints having good all-roundfastness properties, for example light-fastness and wet-fastnessproperties.

It has been shown that the problem posed is largely solved by the noveldyes defined below.

The present invention accordingly relates to reactive dyes of formula(1)

whereinQ₁ and Q₂ are each independently of the other hydrogen or unsubstitutedor substituted C₁-C₄alkyl,A is the radical of a monoazo, polyazo, metal complex azo,anthraquinone, phthalocyanine, formazan or dioxazine chromophore,X is halogen, 3- or 4-carboxypyridin-1-yl, or 3- or4-carbamoylpyridin-1-yl,Y is vinyl or a radical —CH₂—CH₂—U and U is a group removable underalkaline conditions, andq is the number 1 or 2.C₁-C₄alkyl radicals Q₁ and Q₂ are straight-chained or branched. Thealkyl radicals may be further substituted, for example by hydroxy,sulfo, sulfato, cyano or by carboxy. The following radicals may bementioned as examples: methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl and tert-butyl, and also the corresponding radicalssubstituted by hydroxy, sulfo, sulfato, cyano or by carboxy. Preferenceis given to hydroxy, sulfo, sulfato or carboxy as substituents. Specialpreference is given to hydroxy or sulfato as substituent.

Preferably, Q₁ and Q₂ are each independently of the other hydrogen orC₁-C₄alkyl, especially hydrogen, methyl or ethyl, the alkyl radicalsbeing unsubstituted or substituted by hydroxy, sulfo, sulfato or bycarboxy; more especially, Q₁ is hydrogen, and Q₂ is hydrogen, methyl orethyl.

Very especially, Q₁ and Q₂ are hydrogen.

X as halogen is, for example, fluorine, chlorine or bromine, andespecially chlorine or fluorine.

Preferably, X is halogen, and especially chlorine or fluorine.

As a group removable under alkaline conditions, U may be, for example,—Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅,—OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group offormula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, especially—Cl or —OSO₃H, and more especially —OSO₃H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- orβ-chloro-ethyl, β-acetoxy-ethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl. Y in the dye of formula (1)according to the present invention is preferably vinyl, β-chloroethyl orβ-sulfatoethyl, and especially vinyl or β-sulfatoethyl.

Preferably, q is the number 1.

A is, for example, one of the following dye radicals:

a) dye radicals of a 1:1 copper complex azo dye, of the benzene ornaphthalene series, wherein the copper atom is bonded to a group capableof being metallated on either side in the ortho-position to the azobridge;

b) dye radicals of a mono- or dis-azo dye of formula (2) or (3)P₁—N═N-(M-N═N)_(u)—K₁-  (2)or-D₁-N═N-(M-N═N)_(u)—K₁  (3),or of a metal complex derived therefrom, whereinP₁ is the radical of a diazo- or coupling component of the benzene ornaphthalene series, M is the radical of a central component of thebenzene or naphthalene series, K₁ is the radical of a coupling componentof the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one oracetoacetic acid arylamide series, and u is a number 0 or 1, wherein P₁,D₁, M and K₁ may carry substituents customary for azo dyes;c) dye radicals of a disazo dye of formula (4)-D₂-N═N—K₂—N═N-D₃  (4),wherein D₂ and D₃ are each independently of the other the radical of adiazo component of the benzene or naphthalene series, and K₂ is theradical of a coupling component of the naphthalene series, wherein D₂,D₃ and K₂ may carry substituents customary for azo dyes;d) dye radicals of a formazan dye of formula (5)

wherein the benzene rings contain no further substituents or are furthersubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylsulfonyl, halogen orby carboxy;e) dye radicals of an anthraquinone dye of formula (6)

wherein G is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo or is acyclohexylene, phenylenemethylene or C₂-C₆alkylene radical;f) dye radicals of a phthalocyanine dye of formula (7)

wherein Pc is the radical of a metal phthalocyanine, especially theradical of a copper or nickel phthalocyanine, J is —OH and/or —NQ₄Q₅, Q₄and Q₅ are each independently of the other hydrogen or C₁-C₄alkylunsubstituted or substituted by hydroxy or by sulfo, Q₃ is hydrogen orC₁-C₄alkyl, E is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, halogen, carboxy or by sulfo or is a C₂-C₆alkylene radical,and k is from 1 to 3;g) dye radicals of a dioxazine dye of formula (8a), (8b) or (8c)

wherein E′ is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, halogen, carboxy or by sulfo or is a C₂-C₆alkylene radical,v is the number 1, v′ is the number 0 or 1, and the outer benzene ringsin formula (8a), (8b) and (8c) may be further substituted by C₁-C₄alkyl,C₁-C₄alkoxy, acetylamino, nitro, halogen, carboxy, sulfo or by afibre-reactive radical of formula —SO₂—Y, Y being as defined above andhaving the preferred meanings given above.

The expression “substituents customary for azo dyes” is intended toinclude both fibre-reactive and non-fibre-reactive substituents.

The following non-fibre-reactive substituents may be mentioned by way ofexample: C₁-C₄-alkyl, which is to be understood as being methyl, ethyl,n- or iso-propyl, and n-, iso-, sec- or tert-butyl; C₁-C₄alkoxy, whichis to be understood as being methoxy, ethoxy, n- or iso-propoxy, and n-,iso-, sec- or tert-butoxy; hydroxy-C₁-C₄alkoxy; phenoxy;C₂-C₆alkanoylamino unsubstituted or substituted in the alkyl moiety byhydroxy or by C₁-C₄alkoxy, e.g. acetylamino, hydroxyacetylamino,methoxyacetylamino or propionylamino; benzoylamino unsubstituted orsubstituted in the phenyl moiety by hydroxy, sulfo, halogen, C₁-C₄alkylor by C₁-C₄alkoxy; C₁-C₆alkoxycarbonylamino unsubstituted or substitutedin the alkyl moiety by hydroxy, C₁-C₄alkyl or by C₁-C₄alkoxy;phenoxycarbonylamino unsubstituted or substituted in the phenyl moietyby hydroxy, C₁-C₄alkyl or by C₁-C₄alkoxy; amino; N—C₁-C₄alkyl- orN,N-di-C₁-C₄alkyl-amino unsubstituted or substituted in the alkyl moietyby hydroxy, C₁-C₄alkoxy, carboxy, cyano, halogen, sulfo, sulfato, phenylor by sulfophenyl, e.g. methylamino, ethylamino, N,N-dimethylamino,N,N-diethylamino, β-cyanoethylamino, β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, γ-sulfo-n-propylamino,β-sulfatoethylamino, N-ethyl-N-(3-sulfobenzyl)-amino,N—(β-sulfoethyl)-N-benzylamino; cyclohexylamino; N-phenylamino orN—C₁-C₄alkyl-N-phenylamino unsubstituted or substituted in the phenylmoiety by nitro, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, halogen or by sulfo;C₁-C₄alkoxycarbonyl, e.g. methoxy- or ethoxy-carbonyl; trifluoromethyl;nitro; cyano; halogen, which is to be understood generally as being, forexample, fluorine, bromine or, especially, chlorine; ureido; hydroxy;carboxy; sulfo; sulfomethyl; carbamoyl; carbamido; sulfamoyl;N-phenylsulfamoyl or N—C₁-C₄alkyl-N-phenylsulfamoyl unsubstituted orsubstituted in the phenyl moiety by sulfo or by carboxy; methyl- orethyl-sulfonyl.

Fibre-reactive radicals are to be understood as being those which arecapable of reacting with the hydroxy groups of cellulose, with theamino, carboxy, hydroxy and thiol groups in wool and silk or with theamino and possibly carboxy groups of synthetic polyamides to formcovalent chemical bonds. The fibre-reactive radicals are generallybonded to the dye radical directly or via a bridging member. Suitablefibre-reactive radicals are, for example, those having at least oneremovable substituent at an aliphatic, aromatic or heterocyclic radicalor those wherein the mentioned radicals contain a radical suitable forreaction with the fibre material, for example a vinyl radical.

A fibre-reactive substituent present in A corresponds, for example, toformula (9a), (9b), (9c), (9d), (9e), (9f) or (9g)

whereinHal is chlorine or bromine,X₁ is halogen, 3- or 4-carboxypyridin-1-yl, or 3- or4-carbamoylpyridin-1-yl,T₁ has independently the same definitions as X₁, or is anon-fibre-reactive substituent or a fibre-reactive radical of formula(10a), (10b), (10c), (10d), (10e) or (10f)

whereinR₁, R_(1a) and R_(1b) are each independently of the others hydrogen orC₁-C₄alkyl,R₂ is hydrogen, C₁-C₄alkyl unsubstituted or substituted by hydroxy,sulfo, sulfato, carboxy or by cyano, or a radical

R₃ is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen,C₁-C₄alkoxycarbonyl, C₁-C₄alkanoyloxy, carbamoyl or a group —SO₂—Y,alk and alk₁ are each independently of the other linear or branchedC₁-C₆alkylene,arylene is a phenylene or naphthylene radical unsubstituted orsubstituted by sulfo, carboxy, C₁-C₄alkyl, C₁-C₄alkoxy or by halogen,Q is a radical —O— or —NR₁— wherein R₁ is as defined above,W is a group —SO₂—NR₂—, —CONR₂— or —NR₂CO— wherein R₂ is as definedabove,Y being as defined above and having the preferred meanings given above,Y₁ is a group —CH(Hal)-CH₂—Hal or —C(Hal)=CH₂ and Hal is chlorine orbromine, andl and m are each independently of the other an integer from 1 to 6 and nis a number 0 or 1, andX₂ is halogen or C₁-C₄alkylsulfonyl,X₃ is halogen or C₁-C₄alkyl, andT₂ is hydrogen, cyano or halogen.

R₁, R_(1a) and R_(1b) preferably are each independently of the othershydrogen, methyl or ethyl, and especially hydrogen.

R₂ is preferably hydrogen or C₁-C₄alkyl, for example methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, andespecially hydrogen, methyl or ethyl. R₂ is more especially hydrogen.

R₃ is preferably hydrogen.

In the case of the substituents of formulae (9a) and (9c), Y ispreferably vinyl or 6-sulfatoethyl. In the case of the substituent offormulae (9b), Y is preferably β-chloroethyl.

l and m preferably are each independently of the other a number 2, 3 or4, and especially a number 2 or 3.

More especially, l is the number 3 and m is the number 2.

For a non-fibre-reactive substituent T₁ there come into consideration,for example, hydroxy or C₁-C₄alkoxy unsubstituted or substituted in thealkyl moiety, phenoxy unsubstituted or substituted in the phenyl moiety,C₁-C₄alkylthio unsubstituted or substituted in the alkyl moiety,unsubstituted or substituted amino, or an N-heterocycle which may or maynot contain further hetero atoms.

T₁ as a non-fibre-reactive radical is preferably C₁-C₄alkoxy,C₁-C₄alkylthio, hydroxy, amino; N-mono- or N,N-di-C₁-C₄alkylaminounsubstituted or substituted in the alkyl moiety by hydroxy, sulfato orby sulfo; morpholino; or phenylamino or N—C₁-C₄alkyl-N-phenylamino(wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo orby sulfato) each unsubstituted or substituted in the phenyl ring bysulfo, carboxy, acetylamino, chlorine, methyl or by methoxy; ornaphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive radicals T₁ are amino,N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino,2-, 3- or 4-sulfo-phenylamino or N—C₁-C₄alkyl-N-phenylamino.

X₁ is preferably halogen, for example fluorine, chlorine or bromine andespecially chlorine or fluorine.

T₂, X₂ and X₃ as halogen are, for example, fluorine, chlorine orbromine, especially chlorine or fluorine.

X₂ as C₁-C₄alkylsulfonyl is, for example, ethylsulfonyl ormethylsulfonyl and especially methylsulfonyl.

X₃ as C₁-C₄alkyl is, for example, methyl, ethyl, n- or iso-propyl, n-,iso- or tert-butyl and especially methyl.

X₂ and X₃ are preferably each independently of the other chlorine orfluorine.

T₂ is preferably cyano or chlorine.

Hal is preferably bromine.

alk and alk₁ are each independently of the other, for example, amethylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or1,6-hexylene radical or a branched isomer thereof.

alk and alk₁ are preferably each independently of the other aC₁-C₄alkylene radical and especially an ethylene radical or propyleneradical.

arylen is preferably a 1,3- or 1,4-phenylene radical unsubstituted orsubstituted, for example, by sulfo, methyl, methoxy or by carboxy, andespecially an unsubstituted 1,3- or 1,4-phenylene radical.

Q is preferably —NH— or —O— and especially —O—.

W is preferably a group of formula —CONH— or —NHCO—, especially a groupof formula —CONH—.

n is preferably the number 0.

The reactive radicals of formulae (10a) to (10f) are preferably thosewherein W is a group of formula —CONH—, R₁, R₂ and R₃ are each hydrogen,Q is a radical —O— or —NH—, alk and alk₁ are each independently of theother ethylene or propylene, arylene is phenylene unsubstituted orsubstituted by methyl, methoxy, carboxy or by sulfo, Y is vinyl or6-sulfatoethyl, Y₁ is —CHBr—CH₂Br or —CBr═CH₂ and n is the number 0.

A fibre-reactive radical present in A corresponds preferably to aradical of formula (9a), (9b), (9c), (9d), (9e) or (9f), especially(9a), (9b) or (9f), and especially preferred (9a) or (9b),

wherein

Y is vinyl, β-chloroethyl or β-sulfatoethyl,

Hal is bromine,

R₂ and R_(1a) are hydrogen,

m and l are a number 2 or 3,

X₁ is chlorine or fluorine,

T₁ is C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy, amino; N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted in the alkyl moietyby hydroxy, sulfato or by sulfo; morpholino; or phenylamino orN—C₁-C₄alkyl-N-phenylamino (wherein the alkyl is unsubstituted orsubstituted by hydroxy, sulfo or by sulfato) each unsubstituted orsubstituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine,methyl or by methoxy; or naphthylamino unsubstituted or substituted byfrom 1 to 3 sulfo groups, or is a fibre-reactive radical of formula(10a′), (10b′), (10c′), (10d′) or (10f′)

preferably a fibre-reactive radical of formula (10b′) or (10c′), whereinY is as defined above,Y₁ is a group —CH(Br)—CH₂—Br or —C(Br)═CH₂,Me is methyl, and Et is ethyl, and the nitrogen atom in formula (10c′)is substituted by hydrogen, methyl or ethyl, preferably hydrogen orethyl.

In the case of the radicals of formulae (10a′) and (10b′), Y ispreferably β-chloroethyl. In the case of the radicals of formulae (10c′)and (10d′), Y is preferably vinyl or β-sulfatoethyl.

In one embodiment of the present invention A is a radical of a mono-azodye of the formula (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i)or (2j)

wherein (R₄)₀₋₃ denotes from 0 to 3 identical or different substituentsfrom the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo, andZ₁ is a fibre-reactive radical of formula (9a), (9b), (9c), (9d), (9e)or (9f), preferably (9a), (9b) or (9f) and especially (9a) or (9b), thementioned fibre-reactive radicals having the definitions and preferredmeanings given above,

wherein (R₄)₀₋₃ is as defined above,(R₅)₀₋₃ denotes from 0 to 3 identical or different substituents from thegroup halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl,C₁-C₄alkyl; C₁-C₄alkoxy unsubstituted or substituted by hydroxy, sulfatoor by C₁-C₄alkoxy; amino, C₂-C₄alkanoylamino, ureido, hydroxy, carboxy,sulfomethyl, C₁-C₄alkylsulfonylamino, sulfo and a fibre-reactive radicalof the formulae (9b) and (9f), wherein the radicals R_(1a), Y, T₁, X₁and l are as defined above and have the preferred meanings given above,andZ₁ is as defined above and has the preferred meanings given above.

The numbers on the naphthyl rings of the radicals of formulae (2a),(2b), (2e) and (2f) indicate the possible bonding positions.

In another embodiment of the present invention A is a radical of a mono-or dis-azo dye of the formula (2k), (2l), (2m), (2n), (2o), (2p), (2q),(2r), (2s), (2t), (2u), (3a), (3b), (3c), (3d), (3e), (3f), (4a), (4b),(4c) or (4d),

wherein (R₄)₀₋₃ and (R₅)₀₋₃ are as defined above,(R₆)₀₋₃ and (R₈)₀₋₃ denote each independently of the other from 0 to 3identical or different substituents from the group C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy and sulfo,(R₇)₀₋₃ denotes from 0 to 3 identical or different substituents from thegroup C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo, andZ₁ is as defined above and has the preferred meanings given above,

wherein R₉ is sulfophenyl, C₂-C₄alkanoyl, benzoyl or a radical offormula (9b) or (9f) indicated above, wherein the radicals are asdefined above and have the preferred meanings given above, preferablyC₂-C₄alkanoyl or benzoyl,

wherein (R₇)₀₋₃ is as defined above,

wherein R₁₀ and R₁₂ are each independently of the other hydrogen,C₁-C₄alkyl or phenyl, and R₁₁ is hydrogen, cyano, carbamoyl orsulfomethyl,

wherein (R₄)₀₋₃ and Z₁ are in each case as defined above and have thepreferred meanings given above.

The numbers on the naphthyl rings of the radicals of formulae (2k),(2l), (2m), (2n), (2t), (3a), (3b), (3c), (4a), (4b), (4c) and (4d)indicate the possible bonding positions.

The central components of the disazo dye radicals of the formulae (2r)and (2s) are either a benzene or a naphthalene group, which is indicatedby the dotted lines.

Examples of suitable dye radicals A in the reactive dyes according tothe invention are given in U.S. Pat. No. 5,484,899 (columns 13 to 40)and EP-A-0 623 655 (pages 11 to 27).

In an especially preferred embodiment of the dyes according to theinvention, A is a dye radical of the formula (2a), (2b), (2c), (2d),(2e), (2f), (2g), (2h), (2i), (2j) or (6) especially (2b), (2f), (2i),(2j) or (6), wherein

(R₄)₀₋₃, (R₅)₀₋₃, G and Z₁ are in each case as defined above, and

(R₄)₀₋₃ preferably denotes from 0 to 3 identical or differentsubstituents from the group methyl, methoxy and sulfo,

(R₅)₀₋₃ preferably denotes from 0 to 3, especially 0 to 2, identical ordifferent substituents from the group methyl, methoxy, β-hydroxyethoxy,β-sulfatoethoxy, sulfo, acetylamino, ureido, and a fibre-reactiveradical of the formulae (9b),

G preferably is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy or by sulfo,

Z₁ preferably may, if desired, be a fibre-reactive radical of formula(9a) or (9b), wherein Y and l are as defined above and have thepreferred meanings given above.

In a further especially preferred embodiment of the reactive dyesaccording to the invention, A is a dye radical of formula (2k), (2l),(2m), (4a), (4b), (4c) or (4d) indicated above, wherein (R₄)₀₋₃, (R₅)₀₋₃and Z₁ are in each case as defined above and have the preferred meaningsgiven above.

A preferred embodiment of the present invention relates to reactive dyesof formula (1)

wherein

Q₁ and Q₂ are hydrogen,

q is the number 1,

X is chlorine or fluorine,

Y is vinyl, β-chloroethyl or β-sulfatoethyl, and

A is a dye radical of the formula (2b), (2f), (2i), (2j) or (6), wherein

(R₄)₀₋₃ denotes from 0 to 3 identical or different substituents from thegroup C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo, preferablymethyl, methoxy and sulfo,

(R₅)₀₋₃ denotes from 0 to 3 identical or different substituents from thegroup halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl,C₁-C₄alkyl; C₁-C₄alkoxy unsubstituted or substituted by hydroxy, sulfatoor by C₁-C₄alkoxy; amino, C₂-C₄alkanoylamino, ureido, hydroxy, carboxy,sulfomethyl, C₁-C₄alkylsulfonylamino, sulfo and a fibre-reactive radicalof the formulae (9b) and (9f), preferably denotes from 0 to 2, identicalor different substituents from the group methyl, methoxy,β-hydroxyethoxy, β-sulfatoethoxy, sulfo, acetylamino, ureido and afibre-reactive radical of the formulae (9b),G is a phenylene radical unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy or by sulfo,Z₁ is a fibre-reactive radical of formula (9a), (9b) or (9f), especially(9a) or (9b), whereinY is as defined above,R_(1a) is hydrogen,l is the number 3,X₁ is chlorine or fluorine,T₁ is C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy, amino; N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted in the alkyl moietyby hydroxy, sulfato or by sulfo; morpholino; or phenylamino orN—C₁-C₄alkyl-N-phenylamino (wherein the alkyl is unsubstituted orsubstituted by hydroxy, sulfo or by sulfato) each unsubstituted orsubstituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine,methyl or by methoxy; or naphthylamino unsubstituted or substituted byfrom 1 to 3 sulfo groups, or is a fibre-reactive radical of formula(10a′), (10b′), (10c′), (10d′) or (10f′), preferably a fibre-reactiveradical of formula (10b′) or (10c′), whereinY is as defined above,Y₁ is a group —CH(Br)—CH₂—Br or —C(Br)═CH₂,Me is methyl, and Et is ethyl, and the nitrogen atom in formula (10c′)is substituted by hydrogen, methyl or ethyl, preferably hydrogen orethyl.

The present invention relates also to a process for the preparation ofthe reactive dyes of formula (1), wherein q is the number 1, whichcomprises reacting with one another, in any order, approximately onemolar equivalent of an amino dye compound of formula (11a)A-NHQ₁  (11a),or a suitable precursor of the compound of formula (11a), approximatelyone molar equivalent of a compound of formula (12)

and approximately one molar equivalent of a halotriazine, preferably2,4,6-trichloro- or 2,4,6-trifluoro-s-triazine; andto a process for the preparation of the reactive dyes of formula (1),wherein q is the number 2, which comprises reacting with one another, inany order, approximately two molar equivalents of an amino dye compoundof formula (11b)Q₁HN-A-NHQ₁  (11b),or a suitable precursor of the compound of formula (11b), approximatelytwo molar equivalents of a compound of formula (12) as given above, andapproximately two molar equivalents of a halotriazine as given above,or, if using precursors of the compound of formula (11a) or (11b),converting the intermediates obtained into the desired dyes and, whereappropriate, following on with a further transformation reaction, forexample for transformation of a halogen atom on the triazine into anydesired radical X; Q₁, Q₂, A, X and Y in each case being as definedabove and having the preferred meanings given above.

The transformation of intermediates, resulting from the use of aprecursor of the amino dye of formula (11a) or (11b), into the end dyesconsists especially of coupling reactions that result in azo dyes.Coupling to a conventionally diazotised compound is carried outaccording to methods generally known in the art, for example at aneutral to slightly acidic pH and at a temperature of, for example,0-20° C. The diazotisation is effected in customary manner, for exampleusing a nitrite, e.g. an alkali metal nitrite, such as sodium nitrite,in an acid medium, for example a hydrochloric-acid-containing medium, attemperatures of, for example, from −5 to 40° C., preferably from −5 to10° C. and especially from 0 to 5° C.

The halogen atom X on the triazine can be replaced by condensing thecompound of formula (1) obtained wherein X is halogen, preferablyfluorine or chlorine, with a compound X*—H wherein X*has the meaningsgiven above for X except for halogen.

Such condensation reactions are known and described, for example, inEP-A-0 260 227 and U.S. Pat. No. 4,841,049.

The end product may optionally be subjected to a further transformationreaction. Such a transformation reaction is, for example, conversion ofthe radical Y having the meaning —CH₂CH₂—U, wherein U is as definedabove, and a reactive group, present in A and capable of conversion intoa vinyl group, into the vinyl form by treatment with dilute sodiumhydroxide solution, e.g. conversion of the β-sulfatoethylsulfonyl orβ-chloroethylsulfonyl group into the vinylsulfonyl radical. Suchreactions are known per se.

Because the individual process steps mentioned above may be carried outin different orders as well as, where appropriate in some cases,simultaneously, different process variants are possible. The reaction isgenerally carried out in stepwise succession, the order of the simplereactions, known per se, between the individual reaction componentsbeing determined by the particular conditions.

A preferred variant of the preparation of the dyes according to theinvention comprises reacting one molar equivalent of 2,4,6-trichloro- or2,4,6-trifluoro-s-triazine first with one molar equivalent of a compoundof formula (12), if q is the number 1, or reacting two molar equivalentsof 2,4,6-trichloro- or 2,4,6-trifluoro-s-triazine first with two molarequivalents of a compound of formula (12), if q is the number 2, atapproximately neutral pH, for example pH 5-7, and at low temperature,for example 0-5° C., and then reacting the reaction product of formula(13)

obtained, with one molar equivalent of the amino dye of formula (11a),if q is the number 1, or (11 b), if q is the number 2, at a slightlyacidic to neutral pH, for example pH 4.5-6, and at a temperature of, forexample 0-30° C., to form the dye of formula (1), wherein Q₁, Q₂, A, Xand Y in each case being as defined above and having the preferredmeanings given above and X being chlorine or fluorine.

The compounds of formulae (11a), (11 b) and (12) are known per se, theycan be prepared in analogy to known compounds or are commerciallyavailable.

The reactive dyes according to the invention are present either in theform of their free acid or, preferably, in the form of their salts.Suitable salts are, for example, alkali metal, alkaline earth metal orammonium salts or salts of an organic amine. Examples that may bementioned are sodium, lithium, potassium or ammonium salts or a mono-,di- or tri-ethanolamine salt.

The reactive dyes according to the invention are suitable for dyeing andprinting, in particular for printing, a wide variety of materials,especially hydroxyl-group-containing or nitrogen-containing fibrematerials. Examples include paper, silk, leather, wool, polyamide fibresand polyurethanes, and especially all types of cellulosic fibrematerials. Such fibre materials are, for example, natural cellulosefibres, such as cotton, linen and hemp, and cellulose and regeneratedcellulose. The dyes according to the invention are also suitable fordyeing or printing hydroxyl-group-containing fibres present in blendfabrics, for example blends of cotton and polyester fibres or polyamidefibres.

The present invention accordingly relates also to the use of reactivedyes according to the invention in the dyeing or printing ofhydroxyl-group-containing or nitrogen-containing, especiallycotton-containing, fibre materials.

The reactive dyes according to the invention can be applied to the fibrematerial and fixed to the fibre in a variety of ways, especially in theform of aqueous dye solutions or dye print pastes. They are suitableboth for the exhaust process and for dyeing in accordance with thepad-dyeing process; they can be used at low dyeing temperatures andrequire only short steaming times in the pad-steam process. The degreesof fixing are high and unfixed dye can be washed off readily, thedifference between the degree of exhaust and the degree of fixing beingremarkably small, that is to say the soaping loss is very small. Thereactive dyes according to the invention are also suitable for printing,especially on cotton, and also for printing nitrogen-containing fibres,for example wool or silk or blend fabrics that contain wool.

The dyeings and prints produced using the reactive dyes according to theinvention have a high tinctorial strength and a high fibre-dye bindingstability in both the acidic and the alkaline range, and also goodfastness to light and very good wet-fastness properties, such asfastness to washing, to water, to seawater, to cross-dyeing and toperspiration. The dyeings obtained exhibit fibre levelness and surfacelevelness.

The dyes of formula (1) according to the invention are also suitable ascolorants for use in recording systems. Such recording systems are, forexample, commercially available ink-jet printers for paper or textileprinting, or writing instruments, such as fountain pens or ballpointpens, and especially ink-jet printers. For that purpose, the dyesaccording to the invention are first brought into a form suitable foruse in recording systems. A suitable form is, for example, an aqueousink, which comprises the dyes according to the invention as colorants.The inks can be prepared in customary manner by mixing together theindividual components in the desired amount of water.

As substrates there come into consideration the above-mentionedhydroxyl-group-containing or nitrogen-containing fibre materials,especially cotton fibre materials. The fibre materials are preferablytextile fibre materials.

Substrates that also come into consideration are paper and plasticsfilms.

As examples of paper there may be mentioned commercially availableink-jet paper, photo paper, glossy paper, plastics-coated paper, e.g.Epson Ink-jet Paper, Epson Photo Paper, Epson Glossy Paper, Epson GlossyFilm, HP Special Ink-jet Paper, Encad Photo Gloss Paper and Ilford PhotoPaper. Plastics films are, for example, transparent or cloudy/opaque.Suitable plastics films are, for example, 3M Transparency Film.

Depending on the nature of the use, for example textile printing orpaper printing, it may be necessary, for example, for the viscosity orother physical properties of the ink, especially properties that have aninfluence on the affinity for the substrate in question, to be adaptedaccordingly.

The dyes used in the aqueous inks should preferably have a low saltcontent, that is to say they should have a total content of salts ofless than 0.5% by weight, based on the weight of the dyes. Dyes thathave relatively high salt contents as a result of their preparationand/or as a result of the subsequent addition of diluents can bedesalted, for example by membrane separation procedures, such asultrafiltration, reverse osmosis or dialysis.

The inks preferably have a total content of dyes of from 1 to 35% byweight, especially from 1 to 30% by weight and preferably from 1 to 20%by weight, based on the total weight of the ink. The preferred lowerlimit in this case is a limit of 1.5% by weight, preferably 2% by weightand especially 3% by weight.

The inks may comprise water-miscible organic solvents, for exampleC₁-C₄alcohols, e.g. methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol or iso-butanol; amides, e.g.dimethylformamide or dimethylacetamide; ketones or ketone alcohols, e.g.acetone or diacetone alcohol; ethers, e.g. tetrahydrofuran or dioxane;nitrogen-containing heterocyclic compounds, e.g. N-methyl-2-pyrrolidoneor 1,3-dimethyl-2-imidazolidone, polyalkylene glycols, e.g. polyethyleneglycol or polypropylene glycol; C₂-C₆alkylene glycols and thioglycols,e.g. ethylene glycol, propylene glycol, butylene glycol, triethyleneglycol, thiodiglycol, hexylene glycol and diethylene glycol; otherpolyols, e.g. glycerol or 1,2,6-hexanetriol; and C₁-C₄alkyl ethers ofpolyhydric alcohols, e.g. 2-methoxy-ethanol,2-(2-methoxyethoxyl)ethanol, 2-(2-ethoxyethoxyl)ethanol,2-[2-(2-methoxy-ethoxy)ethoxy]ethanol or2-[2-(2-ethoxyethoxyl)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone,diethylene glycol, glycerol or especially 1,2-propylene glycol, usuallyin an amount of from 2 to 30% by weight, especially from 5 to 30% byweight and preferably from 10 to 25% by weight, based on the totalweight of the ink.

In addition, the inks may also comprise solubilisers, e.g.ε-caprolactam.

The inks may comprise thickeners of natural or synthetic origin, interalia for the purpose of adjusting the viscosity.

Examples of thickeners that may be mentioned include commerciallyavailable alginate thickeners, starch ethers or locust bean flourethers, especially sodium alginate on its own or in admixture withmodified cellulose, e.g. methyl cellulose, ethyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethylcellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose,especially with preferably from 20 to 25% by weight carboxymethylcellulose. Synthetic thickeners that may also be mentioned are, forexample, those based on poly(meth)acrylic acids or poly(meth)acrylamidesand also polyalkylene glycols having a molecular weight of, for example,from 2000 to 20 000, such as, for example, polyethylene glycol orpolypropylene glycol or mixed polyalkylene glycols of ethylene oxide andpropylene oxide.

The inks contain such thickeners, for example, in an amount of from 0.01to 2% by weight, especially from 0.01 to 1% by weight and preferablyfrom 0.01 to 0.5% by weight, based on the total weight of the ink.

The inks may also comprise buffer substances, e.g. borax, borates,phosphates, poly-phosphates or citrates. Examples that may be mentionedinclude borax, sodium borate, sodium tetraborate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodiumpentapolyphosphate and sodium citrate. They are used especially inamounts of from 0.1 to 3% by weight, preferably from 0.1 to 1% byweight, based on the total weight of the ink, in order to establish a pHvalue of, for example, from 4 to 9, especially from 5 to 8.5.

As further additives, the inks may comprise surfactants or humectants.

Suitable surfactants include commercially available anionic or non-ionicsurfactants. As humectants in the inks according to the invention therecome into consideration, for example, urea or a mixture of sodiumlactate (advantageously in the form of a 50% to 60% aqueous solution)and glycerol and/or propylene glycol in amounts of preferably from 0.1to 30% by weight, especially from 2 to 30% by weight.

Preference is given to inks having a viscosity of from 1 to 40 mPa·s,especially from 1 to 20 mPa·s and more especially from 1 to 10 mPa·s.

Furthermore, the inks may in addition comprise customary additives, e.g.anti-foams or especially preservatives that inhibit fungal and/orbacterial growth. Such additives are usually used in amounts of from0.01 to 1% by weight, based on the total weight of the ink.

As preservatives there come into consideration formaldehyde-yieldingagents, for example paraformaldehyde and trioxane, especially aqueous,approximately from 30 to 40% by weight formaldehyde solutions, imidazolecompounds, for example 2-(4-thiazolyl)-benzimidazole, thiazolecompounds, for example 1,2-benzisothiazolin-3-one or2-n-octyl-isothiazolin-3-one, iodine compounds, nitriles, phenols,haloalkylthio compounds or pyridine derivatives, especially1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one. A suitablepreservative is, for example, a 20% by weight solution of1,2-benzisothiazolin-3-one in dipropylene glycol (Proxel® GXL).

The inks may in addition comprise further additives, such as fluorinatedpolymers or telomers, for example polyethoxyperfluoroalcohols (Forafac®or Zonyl® products) in an amount of, for example, from 0.01 to 1% byweight, based on the total weight of the ink.

In the case of the ink-jet printing method, individual droplets of inkare sprayed onto a substrate from a nozzle in a controlled manner. It ismainly the continuous ink-jet method and the drop-on-demand method thatare used for that purpose. In the case of the continuous ink-jet method,the droplets are produced continuously, droplets not required for theprinting operation being discharged into a receptacle and recycled. Inthe case of the drop-on-demand method, on the other hand, droplets aregenerated as desired and used for printing; that is to say, droplets aregenerated only when required for the printing operation. The productionof the droplets can be effected, for example, by means of a piezoink-jet head or by thermal energy (bubble jet). Preference is given toprinting by means of a piezo ink-jet head and to printing according tothe continuous ink-jet method.

The present invention accordingly relates also to aqueous inks thatcomprise the dyes of formula (1) according to the invention and to theuse of such inks in an ink-jet printing method for printing a variety ofsubstrates, especially textile fibre materials, the definitions andpreferences indicated above applying to the dyes, the inks and thesubstrates.

The dyes of the present invention show very good build-up behaviour, ahigh end build-up and a high degree of fixation, especially in printingapplications on cellulosic fibre materials.

The following Examples serve to illustrate the invention. Unlessotherwise indicated, the temperatures are given in degrees Celsius,parts are parts by weight and percentages relate to percent by weight.Parts by weight relate to parts by volume in a ratio of kilograms toliters.

EXAMPLE 1

(a) 3.76 g (0.0204 mol) of cyanuric chloride are suspended into 40 ml ofwater and 40 g of ice. The resulting suspension is then cooled to 0-5°C. using an external ice water bath. 5 ml of a 10% aqueous solution ofdisodiumhydrogenphosphate and 0.5 ml of a conventional dispersing agent(Sandozin NE from Clariant) are then added to the suspension. Theresulting suspension is stirred at 0-5° C. until further use.(b) 7.55 g (0.02 mol) of 2-(2-Amino-6-sulfo-phenol-4-sulfonyl)ethylsulfate are mixed in 80 ml of water and 60 g of ice. A temperature of0-5° C. is adjusted and maintained using an external ice water bath. ThepH is adjusted to 6.0 by addition of an aqueous sodium hydroxydesolution (30%). The resulting yellowish-brown solution is then stirredat 0-5° C. for 30 minutes.(c) The solution obtained according to step (b) is added to the cyanuricchloride solution obtained according to step (a) over 30 minutes at a pHof 5.0-6.0 and a temperature of 0-5° C. The pH is maintained at around5.0-6.0 by addition of an aqueous sodium carbonate solution (20%). After45 minutes, the first condensation step is completed. The pH is loweredto 4.5 by addition of hydrochloric acid (32%) before submitting thesolution to the procedure described in step (e).(d) 12.0 g (0.02 mol) of the amino formazan dye of formula

are solubilized in 150 ml of water at 20° C., and at pH 4.5, and stirreduntil further use.e) The solution obtained according to step (c) is added to the formazansolution obtained according to step (d) over 30 minutes at 20° C., andat pH 4.5. The pH is kept constant by the addition of hydrochloric acid(32%). After the addition is complete, the resulting solution is heatedto 40° C. and stirred at this temperature for 3.5 hours, while the pH iskept constant by means of an aqueous sodium carbonate solution (20%).After completion of the reaction, the reaction mixture is cooled to 20°C. and the pH is adjusted to 7.0 by addition of an aqueous sodiumcarbonate solution (20%). The solution is submitted to a reverse osmosisfor 12 hours and then dried, providing 25.6 g of a dyestuff as a bluepowder, which in its free acid form corresponds to the formula

having a λ_(max) of 610 nm.

EXAMPLE 2

(a) 6.1 g (0.019 mol) of 1-amino-8-hydroxy-3,6-disulfonaphthalene(H-Acid) are suspended into 100 ml of water at 20° C. The pH is adjustedto 6.0-7.0 by addition of an aqueous sodium hydroxyde solution (30%),and the mixture is then stirred until H-Acid is completely dissolved.(b) The solution obtained according to step (a) of this Example 2 isadded to a solution prepared in accordance with Example 1(c) at pH 2.0and a temperature of 5-10° C. The pH is then raised slowly to pH 4.0 byaddition of an aqueous sodium carbonate solution (20%). Once pH 4 isreached, the temperature is raised to 25-30° C. and the mixture isstirred at this temperature for 6 hours, while the pH is kept constantby addition of an aqueous sodium carbonate solution (20%). Aftercompletion of the reaction, the solution is kept as it is until furtheruse. The pH is raised to 7.0-7.5 by addition of an aqueous sodiumcarbonate solution (20%), before submitting the solution to theprocedure described in step (d).(c) 6.1 g (0.02 mol) of 1,5-disulfo-2-aminonaphthalene are suspendedinto 100 ml water and dissolved at pH 2.0 by addition of an aqueoussodium hydroxyde solution (30%). Once dissolved, the pH is lowered below1.0 by addition of hydrochloric acid (32%), and 30 g of ice are added tocool the mixture to 0-5° C. The temperature is kept constant by using anexternal ice-water bath. 5.25 ml of sodium nitrite 4 N are added and themixture is stirred for 30 minutes. After completion of the diazotationreaction, excess of sodium nitrite is destroyed with sulfamic acid.(d) The solution obtained according to step (b) of this Example 2 iscooled by means of an external ice-water bath, and the pH is adjusted to7.0-7.5. The ice-water bath is removed and the diazonium salt solutionaccording to step (c) of this Example 2 is added over 20 minutes atabout 10° C., while the pH is kept at 7.5-8.0 by addition of an aqueoussodium carbonate solution (20%). The temperature is then allowed toincrease to 20° C. After completion of the reaction, the pH is adjustedto 7.0 by addition of hydrochloric acid (32%). The solution is submittedto a reverse osmosis for 12 hours and then dried, providing 25.5 g of adyestuff as a red powder, which in its free acid form corresponds to theformula

having a λ_(max) of 542/524 nm.

EXAMPLE 3

(a) 11.1 g (0.02 mol) of a amino monoazo dye of formula

are solubilized in 100 ml of water at 20° C. The pH is adjusted to4.0-4.5 by addition of an aqueous sodium hydroxyde solution (30%) Theorange solution is then stirred until further use.(b) The solution obtained according to step (a) of this Example 3 isadded to a solution prepared in accordance with Example 1(c) at pH4.0-4.5 and a temperature of 5-10° C. over 15 minutes. After theaddition is complete, the temperature is raised to 35-40° C. and themixture is stirred at this temperature for 5 hours while the pH is keptconstant by addition of an aqueous sodium carbonate solution (20%).After completion of the reaction, the solution is cooled to 20° C. andpH is adjusted to 7.0 by addition of an aqueous sodium carbonatesolution (20%). The solution is submitted to a reverse osmosis for 12hours and then dried, providing 27.3 g of a dyestuff as an orangepowder, which in its free acid form corresponds to the formula

having a λ_(max) of 486 nm.

EXAMPLES 4 TO 53

The dyestuffs indicated in Table 1 can be prepared analogously to theprocedures described in Examples 1, 2 and 3.

TABLE 1 Exam- Color λ_(max) ple shade [nm] 4

Lemon Yellow 422 5

Lemon yellow 424 6

Orange 426 7

Red 520 8

Red 504 9

Red 510 10

Turquois 628/670 11

Navy 626 12

Navy 606 13

Navy 612 14

Red 548/524 15

Bordeaux 532 16

Orange 474 17

Blue 604 18

Blue 606 19

Scarlet 492 20

Orange 488 21

Scarlet 500 22

Orange 482 23

Orange 442 24

Blue 616 25

Blue 600 26

Yellow 384 27

Red 520 28

Red 540 29

Red 542/520 30

Violet 542 31

Orange 400 32

Violet 560 33

Blue 614 34

Yellow 414 35

Red 526 36

Red 514 37

Red 542 38

Orange 428 39

Red 524 40

Yellow 442 41

Red Brown 490 42

Golden Yellow 424 43

Yellow 382 44

Golden Yellow 398 45

Golden Yellow 410 46

Royal Blue 592 47

Royal Blue 596 48

Brilliant Blue 586 49

Brilliant Blue 586 50

Golden Yellow 408 51

Red 532/516 52

Navy 614 53

Grey 580Dyeing Instructions I:

2 parts of the dye obtained according to Example 1 are dissolved in 400parts of water; 1500 parts of a solution which comprises 53 g of sodiumchloride per liter are added. 100 parts of cotton fabric are introducedinto this dyebath at 40° C. After 45 minutes, 100 parts of a solutionwhich comprises 16 g of sodium hydroxide and 20 g of calcined sodiumcarbonate per liter are added. The temperature of the dyebath is kept at40° C. for a further 45 minutes. Thereafter, the dyed goods are rinsed,soaped at the boil with a non-ionic detergent for a quarter of an hour,rinsed again and dried.

Dyeing Instructions II:

2 parts of the reactive dye obtained according to Example 1 aredissolved in 400 parts of water; 1500 parts of a solution whichcomprises 53 g of sodium chloride per liter are added. 100 parts ofcotton fabric are introduced into this dyebath at 35° C. After 20minutes, 100 parts of a solution which comprises 16 g of sodiumhydroxide and 20 g of calcined sodium carbonate per liter are added. Thetemperature of the dyebath is kept at 35° C. for a further 15 minutes.Thereafter, the temperature is increased to 60° C. in the course of 20minutes. The temperature is kept at 60° C. for a further 35 minutes.Thereafter, the goods are rinsed, soaped at the boil with a non-ionicdetergent for a quarter of an hour, rinsed again and dried.

Dyeing Instructions III:

8 parts of the reactive dye obtained according to Example 1 aredissolved in 400 parts of water; 1400 parts of a solution whichcomprises 100 g of sodium sulfate per liter are added. 100 parts ofcotton fabric are introduced into this dyebath at 25° C. After 10minutes, 200 parts of a solution which comprises 150 g of trisodiumphosphate per liter are added. Thereafter, the temperature of thedyebath is increased to 60° C. in the course of 10 minutes. Thetemperature is kept at 60° C. for a further 90 minutes. Thereafter, thegoods are rinsed, soaped at the boil with a non-ionic detergent for aquarter of an hour, rinsed again and dried.

Dyeing Instructions IV:

4 parts of the reactive dye obtained according to Example 1 aredissolved in 50 parts of water. 50 parts of a solution which comprises 5g of sodium hydroxide and 20 g of calcined sodium carbonate per literare added. A cotton fabric is padded with the resulting solution suchthat it increases by 70% of its weight, and is then wound onto a roll.The cotton fabric is stored in this manner at room temperature for 3hours. The dyed goods are then rinsed, soaked at the boil with anon-ionic detergent for a quarter of an hour, rinsed again and dried.

Dyeing Instructions V:

6 parts of the reactive dye obtained according to Example 1 aredissolved in 50 parts of water. 50 parts of a solution which comprises16 g of sodium hydroxide and 0.04 liter of water-glass (38° be) perliter are added. A cotton fabric is padded with the resulting solutionsuch that it increases by 70% of its weight, and is then wound onto aroll. The cotton fabric is stored in this manner at room temperature for10 hours. The dyed goods are then rinsed, soaped at the boil with anon-ionic detergent for a quarter of an hour, rinsed again and dried.

Dyeing Instructions VI:

2 parts of the reactive dye obtained according to Example 1 aredissolved in 100 parts of water with the addition of 0.5 part of sodiumm-nitrobenzene sulfonate. A cotton fabric is impregnated with theresulting solution such that it increases by 75% of its weight, and isthen dried. The fabric is then impregnated with a solution, warmed to20° C., which comprises 4 g sodium hydroxide and 300 of sodium chlorideper liter and squeezed off to a weight increase of 75%, and the dyeingis then steamed at 100 to 102° C. for 30 seconds, rinsed, soaped for aquarter of an hour in a 0.3% boiling solution of a non-ionic detergent,rinsed and dried.

Printing Instructions I:

3 parts of the reactive dye obtained according to Example 1 aresprinkled with high-speed stirring into 100 parts of a stock thickenercomprising 50 parts of 5% sodium alginate thickener, 27.8 parts ofwater, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and1.2 parts of sodium bicarbonate. A cotton fabric is printed with theprinting paste thus obtained and dried and the printed material obtainedis steamed in saturated steam at 102° C. for 2 minutes. The printedfabric is then rinsed, soaped at the boil and rinsed again, ifappropriate, and then dried.

Printing Instructions II:

5 parts of the reactive dye obtained according to Example 51 aresprinkled with high-speed stirring into 100 parts of a stock thickenercomprising 50 parts of 5% sodium alginate thickener, 36.5 parts ofwater, 10 parts of urea, 1 part of m sodium m-nitrobenzene sulfonate and2.5 parts of sodium bicarbonate. A mercerised cotton satin fabric isprinted with the printing paste thus obtained, the stability of whichmeets the technical requirements, and the resulting printed material issteamed in saturated steam at 102° C. for 8 minutes. The printed fabricis then rinsed, soaped at the boil and rinsed again, if appropriate, andthen dried.

Build-up of the dyes according to the present invention and prior artdyes of similar structure is studied according to common practice in theart by preparing and applying printing pastes containing differentdyestuff concentrations in accordance with the above printinginstructions II. Mercerised cotton satin fabrics are printed using thepastes prepared. The reference depths of the printed fabrics aremeasured photospectrometrically. The build-up diagrams are prepared andthe maximum build-up is determined in the usual manner. Furthermore, thedegree of fixation is determined in the usual manner by cutting aspecimen of the printed fabric of defined size and dissolving/extractingthe unfixed dyestuff with a phosphate buffered aqueous solution (pH 7)at the boil. The reference fabric is prepared by printing withoutsteaming in saturated steam. The following results are obtained:

Dyestuff of Example 29 of the formula  

E₂₅*: 0.46 Degree of fixation: 80% Max build-up 1.90 RD** Dyestuff offormula  

E₂₅*: 0.61 Degree of fixation 66% Max build-up 1.64 RD** Dyestuff ofExample 47 of formula  

E₂₅*: 0.28 Max build-up 1.40 RD** Dyestuff of formula  

E₂₅*: 0.24 Max build-up 1.14 RD** Dyestuff of Example 51 of the formula 

E₂₅*: 0.61 Degree of fixation: 66% Max build-up 2.60 RD** Dyestuff offormula  

E₂₅*: 0.71 Degree of fixation: 55% Max build-up 1.66 RD** *E₂₅ means theextinction at λ_(max)/c = 25 mg/l **RD means Reference Depth

The dyes according to the present invention show superior build-up and ahigher degree of fixation than the dyes of the prior art.

Printing Instructions III:

(a) Mercerised cotton satin is pad-dyed with a liquor containing 30 g/lof sodium carbonate and 50 g/l of urea (70% liquor pick-up) and dried.

(b) Using a drop-on-demand ink-jet head (bubble jet), the cotton satinpretreated according to Step (a) is printed with an aqueous inkcontaining

-   -   15% by weight of the reactive dye according to Example 1,    -   15% by weight of 1,2-propylene glycol and    -   70% by weight of water.

The print is dried completely and fixed in saturated steam for 8 minutesat 102° C., cold-rinsed, washed off at the boil, rinsed again and dried.

What is claimed is:
 1. A reactive dye of formula (1)

wherein Q₁ and Q₂ are each independently of the other hydrogen orunsubstituted or substituted C₁-C₄ alkyl, A is the radical of a monoazo,polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan ordioxazine chromophore, X is halogen, 3- or 4-carboxypyridin-1-yl, or 3-or 4-carbamoylpyridin-1-yl, Y is vinyl or a radical —CH₂—CH₂—U and U is—Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄ alkyl)₂, and q is the number 1 or
 2. 2. Areactive dye according to claim 1, wherein Q₁ and Q₂ are hydrogen.
 3. Areactive dye according to claim 1, wherein X is fluorine or chlorine. 4.A reactive dye according to claim 1, wherein U is —Cl, —OSO₃H, —SSO₃H,—OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂.
 5. A reactive dye according to claim 1,wherein q is the number
 1. 6. A reactive dye according to claim 1,wherein A is a radical of a mono-azo dye selected from the groupconsisting of the formulae (2a), (2b), (2c), (2d), (2e), (2f), (2g),(2h), (2i), (2j) and (6)

wherein (R₄)₀₋₃ denotes from 0 to 3 identical or different substituentsselected from the group consisting of C₁-C₄ alkyl, C₁-C₄ alkoxy,halogen, carboxy and sulfo, and Z₁ is a fibre-reactive radical offormula (9a), (9b) or (9f)

wherein Y is vinyl or a radical —CH₂—CH₂—U and U is —Cl or —OSO₃H,R_(1a) is hydrogen, l is the number 3, X₁ is chlorine or fluorine, T₁ isa fibre-reactive radical of formula (10b′) or (10c′)

wherein Me is methyl, and Et is ethyl, and the nitrogen atom in formula(10c′) is substituted by hydrogen, methyl or ethyl, (R₅)₀₋₃ denotes from0 to 3 identical or different substituents selected from the groupconsisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁-C₄ alkyl; C₁-C₄ alkoxy unsubstituted or substituted byhydroxy, sulfato or by C₁-C₄ alkoxy; amino, C₂-C₄ alkanoylamino, ureido,hydroxy, carboxy, sulfomethyl, C₁-C₄ alkylsulfonylamino, sulfo and afibre-reactive radical of the formulae (9b) and (9f), wherein theradicals R_(1a), Y, T₁, X₁ and l are as defined above, and G is aphenylene radical unsubstituted or substituted by C₁-C₄ alkyl, C₁-C₄alkoxy or by sulfo.
 7. A reactive dye according to claim 1, wherein A isa dye radical of formula (2k), (2l), (2m), (4a), (4b), (4c) or (4d),

wherein (R₄)₀₋₃ denotes from 0 to 3 identical or different substituentsselected from the group consisting of C₁-C₄ alkyl, C₁-C₄ alkoxy,halogen, carboxy and sulfo, and Z₁ is a fibre-reactive radical offormula (9a), (9b) or (9f)

wherein Y is vinyl or a radical —CH₂—CH₂—U and U is —Cl or —OSO₃H,R_(1a) is hydrogen, l is the number 3, X₁ is chlorine or fluorine, T₁ isa fibre-reactive radical of formula (10b′) or (10c′)

wherein Me is methyl, and Et is ethyl, and the nitrogen atom in formula(10c′) is substituted by hydrogen, methyl or ethyl, (R₅)₀₋₃ denotes from0 to 3 identical or different substituents selected from the groupconsisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁-C₄ alkyl; C₁-C₄ alkoxy unsubstituted or substituted byhydroxy, sulfato or by C₁-C₄ alkoxy; amino, C₂-C₄ alkanoylamino, ureido,hydroxy, carboxy, sulfomethyl, C₁-C₄ alkylsulfonylamino, sulfo and afibre-reactive radical of the formulae (9b) and (9f), wherein theradicals R_(1a), Y, T₁, X₁ and l are as defined above.
 8. A reactive dyeaccording to claim 1, wherein Q₁ and Q₂ are hydrogen, q is the number 1,X is chlorine or fluorine, Y is vinyl, β-chloroethyl or β-sulfatoethyl,and A is a dye radical of the formula (2b), (2f), (2i), (2j) or (6),

wherein (R₄)₀₋₃ denotes from 0 to 3 identical or different substituentsselected from the group consisting of C₁-C₄ alkyl, C₁-C₄ alkoxy,halogen, carboxy and sulfo, and Z₁ is a fibre-reactive radical offormula (9a), (9b) or (9f)

wherein Y is vinyl or a radical —CH₂—CH₂—U and U is —Cl or —OSO₃H,R_(1a) is hydrogen, l is the number 3, X₁ is chlorine or fluorine, T₁ isa fibre-reactive radical of formula (10b′) or (10c′)

wherein Me is methyl, and Et is ethyl, and the nitrogen atom in formula(10c′) is substituted by hydrogen, methyl or ethyl, (R₅)₀₋₃ denotes from0 to 3 identical or different substituents selected from the groupconsisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁-C₄ alkyl; alkoxy unsubstituted or substituted by hydroxy,sulfato or by C₁-C₄ alkoxy; amino, C₂-C₄ alkanoylamino, ureido, hydroxy,carboxy, sulfomethyl, alkylsulfonylamino, sulfo and a fibre-reactiveradical of the formulae (9b) and (9f), wherein the radicals R_(1a), Y,T₁, X₁ and 1 are as defined above, and G is a phenylene radicalunsubstituted or substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy or by sulfo.9. A process for the preparation of the reactive dye of formula (1) ofclaim 1, wherein q is the number 1, which comprises reacting with oneanother, in any order, approximately one molar equivalent of an aminodye compound of formula (11a)A-NHQ₁  (11a), approximately one molar equivalent of a compound offormula (12)

and approximately one molar equivalent of a halotriazine, wherein Q₁,Q₂, A, X and Y in each case being as defined in claim
 1. 10. A processfor the preparation of the reactive dye of formula (1) of claim 1,wherein q is the number 2, which comprises reacting with one another, inany order, approximately two molar equivalents of an amino dye compoundof formula (11b)Q₁HN-A-NHQ₁  (11b), approximately two molar equivalents of a compound offormula (12)

and approximately two molar equivalents of a halotriazine wherein Q₁,Q₂, A, X and Y in each case being as defined in claim
 1. 11. A processfor dyeing or printing hydroxyl-group containing or nitrogen-containingfibre material comprising applying the reactive dye of formula (1) ofclaim 1 to fibre material.
 12. The process of claim 11, wherein thefibre material is a cotton material.